CN104076605A - Curable composition for printed wiring board, cured coating film prepared from curable composition, and printed wiring board - Google Patents
Curable composition for printed wiring board, cured coating film prepared from curable composition, and printed wiring board Download PDFInfo
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- CN104076605A CN104076605A CN201410124536.4A CN201410124536A CN104076605A CN 104076605 A CN104076605 A CN 104076605A CN 201410124536 A CN201410124536 A CN 201410124536A CN 104076605 A CN104076605 A CN 104076605A
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- methyl
- circuit board
- printed circuit
- curing composition
- acrylate compounds
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0393—Flexible materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/01—Tools for processing; Objects used during processing
- H05K2203/0104—Tools for processing; Objects used during processing for patterning or coating
- H05K2203/013—Inkjet printing, e.g. for printing insulating material or resist
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
A curable composition to be used for a printed wiring board is disclosed, which has an excellent flexibility and an excellent adhesive property with respect to both a plastic substrate and a conductive layer in the printed wiring board. The curable composition includes (A) a (meth)acrylate compound having a polyene structure, (B) a (meth)acrylate compound having a hydroxyl group; and (C) a photopolymerization initiator. From the curable composition, a cured coating film, and a printed wiring board including the cured coating film in the form of a predetermined pattern are obtained.
Description
Technical field
The present invention relates to the curing composition of use in printed circuit board, the use in printed circuit board cured coating films such as composition, the resist layer that uses it, mark layer and etch layer of the ultraviolet hardening that particularly uses by ink-jetting style and the figuratum printed circuit board (PCB) of tool that uses it to obtain.
Background technology
For example, as flexible printed circuit board, band, carry the resist using in the manufacture of packaging body, known have: after (1) is used and is called as the Kapton of coverlay with the corresponding Dies ' Blanking of pattern, use bonding agent by its stickup and make its curing type (for example patent documentation 1); (2) utilizing serigraphy coating to be used to form has the light-cured type composition of flexible epithelium and makes its curing type (for example patent documentation 2); (3) coating is used to form and has photocuring/thermohardening type resin combination of flexible epithelium and make its exposure, development, curing type (for example patent documentation 3).Wherein, (2) type that process number is few, the productive temp time (takt time) is fast while preferably using pattern to form, is especially preferably used the curability composition of curing type faster.
Prior art document
Patent documentation
Patent documentation 1: No. 5-75032, Japanese Patent Publication
Patent documentation 2: No. 10-224018, Japanese kokai publication hei
Patent documentation 3: No. 9-54434, Japanese kokai publication hei
Summary of the invention
the problem that invention will solve
For curing composition as described above, need to maintain each characteristics such as resistance to sweating heat performance and guarantee for using polyimide etc. as the plastic base of principal ingredient with the adaptation of the conductor circuit metal arranging thereon.Yet, utilize in patent documentation 2 the existing light-cured type composition of recording and the shortage flexibility of filming forming is difficult to obtain the excellent adaptation to conducting channel metal and plastic base, therefore expectation improves.
The present invention makes in order to eliminate above-mentioned prior art problem, and its fundamental purpose is, provide each characteristics such as maintaining resistance to sweating heat performance and flexibility excellent, with the curing composition of the adaptation excellence of plastic base and conductor layer.
Other object of the present invention is, provides and uses described use in printed circuit board curing composition to form, guaranteed the pattern cured of the excellent adaptation of plastic basis material and conducting channel metal film and have the printed circuit board (PCB) of the pattern that use in printed circuit board curing composition is solidified and obtain.
for the scheme of dealing with problems
Find that above-mentioned purpose of the present invention can utilize following use in printed circuit board curing composition to reach, described use in printed circuit board curing composition is characterised in that, comprises:
Have polyenoid skeleton (methyl) acrylate compounds,
Have hydroxyl (methyl) acrylate compounds and
Photoepolymerizationinitiater initiater.
; use in printed circuit board curing composition of the present invention is characterised in that, comprises: (A) have (methyl) acrylate compounds of polyenoid skeleton, (methyl) acrylate compounds that (B) has hydroxyl and (C) Photoepolymerizationinitiater initiater.
About use in printed circuit board curing composition of the present invention, preferably, the polyenoid skeleton (A) having in (methyl) acrylate compounds of polyenoid skeleton is formed by the polymerization of butadiene and/or isoprene.
And then the polyenoid skeleton of (methyl) acrylate compounds (A) preferably consists of the repetitive shown in (I).
(in formula, n represents 10～300.)
And then use in printed circuit board curing composition of the present invention preferably comprises except having 2 officials of hydroxyl, 2 officials' energy (methyl) acrylate compounds can (methyl) acrylate compounds.Should be preferably 5～50mPas except thering is 2 officials energy (methyl) acrylate compounds viscosity 25 ℃ at of 2 officials of hydroxyl can (methyl) acrylate compounds.
And then use in printed circuit board composition of the present invention preferably also comprises heat curing composition.
And then the viscosity of printed circuit board (PCB) curing composition of the present invention at 50 ℃ is preferably 5～50mPas.
Cured coating film of the present invention is characterised in that, by above-mentioned use in printed circuit board curing composition is carried out to irradiation, obtains.
Printed circuit board (PCB) of the present invention is characterised in that to have pattern cured and film, and described pattern cured is filmed by utilizing ink jet printing method that above-mentioned printed circuit board (PCB) curing composition is printed onto on substrate and it being carried out to irradiation obtains.
About printed circuit board (PCB) of the present invention, preferably, aforesaid substrate is plastic base.
the effect of invention
According to the present invention, can access each characteristics such as maintaining resistance to sweating heat performance and be imbued with flexibility, plastic base and conductor circuit metal are there is to the cured coating film of excellent adaptation.In addition, curing composition of the present invention can be used as ink-jet composition aptly.
Embodiment
Use in printed circuit board curing composition of the present invention (following, also referred to as curing composition) comprises: (A) have (methyl) acrylate compounds (composition A) of polyenoid skeleton, (methyl) acrylate compounds (composition B) that (B) has hydroxyl and (C) Photoepolymerizationinitiater initiater (composition C).
It should be noted that, in this manual, (methyl) acrylate refers to the term of general designation acrylate, methacrylate and their potpourri, for other, similarly shows too.
[(methyl) acrylate compounds (A) with polyenoid skeleton]
The polyenoid skeleton of (methyl) acrylate compounds (composition A) preferably, by for example using butadiene or isoprene or their both polymerizations to form, particularly preferably consists of the repetitive shown in general formula (I).Due to the olefinic double bond of such repetitive, can give use in printed circuit board curing composition flexibility, the tracing ability of base material is increased, can obtain good adaptation.
(in formula, n represents 10～300.)
About the polyenoid skeleton of above-mentioned (methyl) acrylate compounds (composition A), the repetitive shown in above-mentioned general formula I is preferably more than 50%, more preferably more than 80%.
And then the polyenoid skeleton of (methyl) acrylate compounds (composition A) also can contain the unit shown in following general formula (II).
The molecular weight with (methyl) acrylate compounds (composition A) of polyenoid skeleton is made as 700～15000 scope conventionally, preferably in 1000～12000 scope.
As object lesson, preferably use following material.That is, have: by the hydroxyl that (methyl) acrylic acid 2-hydroxyl ethyl ester is situated between by 2,4-toluene diisocyanate and liquid polybutadiene, carry out carbamate addition reaction and liquid polybutadiene carbamate (methyl) acrylate that obtains;
The liquid polybutadiene acrylate that makes maleinization polybutadiene (maleated polybutadiene) that 2-hydroxy acrylate and addition maleic anhydride form carry out esterification and obtain;
Liquid polybutadiene (methyl) acrylate obtaining by the carboxyl of maleinization polybutadiene and the epoxidation esterification of (methyl) glycidyl acrylate;
By making epoxidizing agent act on liquid polybutadiene (methyl) acrylate that epoxidized polybutadiene that liquid polybutadiene obtains and (methyl) acrylic acid esterification obtain;
Liquid polybutadiene (methyl) acrylate obtaining by thering is the liquid polybutadiene of hydroxyl and the dechlorination reaction of (methyl) acryloyl chloride;
The liquid hydrogenation 1 that the unsaturated double-bond hydrogenation at molecule two ends with the liquid polybutadiene of hydroxyl is formed, 2-polybutadiene diol is carried out the acrylate modified and liquid hydrogenation 1 that obtains of carbamate (methyl), 2-polybutadiene (methyl) acrylate etc.
Example as commercially available product, can list NISSO PB TE-2000, NISSO PB TEA-1000, NISSO PB TE-3000, NISSO PB TEAI-1000 (are NIPPON SODA CO. above, LTD. manufacture), CN301, CN303, CN307 (Sartomer Company manufacture), BAC-15 (OSAKA ORGANIC CHEMICAL INDUSTRY LTD. manufacture), BAC-45 (OSAKA ORGANIC CHEMICAL INDUSTRY LTD. manufacture), EY RESIN BR-45UAS (Light Chemical Industries Co., Ltd. manufactures) etc.
The compounding amount with (methyl) acrylate compounds (composition A) of polyenoid skeleton is 3～70 quality % in composition, be preferably 10～45 quality %.
While having (methyl) acrylate compounds less than 3 quality % of polyenoid skeleton, existence can not obtain the situation to the adaptation of substrate as the feature of composition of the present invention, therefore not preferred.On the other hand, when compounding amount surpasses 70 quality %, there is the situation of black component separating, therefore not preferred.
(A) (methyl) acrylate compounds that has a polyenoid skeleton can be used a kind or be used in combination multiple.
[(methyl) acrylate compounds (B) with hydroxyl]
(methyl) acrylate compounds (B) with hydroxyl of composition B is used the low-molecular-weight materials such as monomer or oligomer, particularly, use the material of the scope of molecular weight 100～1000, preferably use the material of the scope of molecular weight 110～700.
The object lesson as (B) with (methyl) acrylate compounds of hydroxyl, can list (methyl) acrylic acid 2-hydroxyl-3-acryloxy propyl ester, (methyl) acrylic acid 2-hydroxyl-3-phenoxy ethyl, 1,4-CHDM list (methyl) acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 4-hydroxy butyl ester, pentaerythrite three (methyl) acrylate, dipentaerythritol monohydroxy five (methyl) acrylate, (methyl) acrylic acid 2-hydroxypropyl acrylate etc.As commercially available product, there are ARONIX M-5700 (trade name that Toagosei Co., Ltd manufactures), 4HBA, 2HEA, CHDMMA (being Nippon Kasei Chemical Co. above, the trade name that Ltd manufactures), BHEA, HPA, HEMA, HPMA (trade name of manufacturing for Nippon Shokubai Co., Ltd above), Light Ester HO, Light Ester HOP, Light Ester HOA (trade name of manufacturing for Kyoeisha Chemical Co., Ltd. above) etc.(B) (methyl) acrylate compounds that has a hydroxyl can be used a kind or be used in combination multiple.
Wherein, particularly preferably use acrylic acid 2-hydroxyl-3-acryloxy propyl ester, acrylic acid 2-hydroxyl-3-phenoxy ethyl, acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate, acrylic acid 4-hydroxy butyl ester, 1,4-CHDM mono acrylic ester.
(B) the compounding amount that has (methyl) acrylate of hydroxyl is preferably 5～50 mass parts, 10～30 mass parts more preferably with respect to 100 mass parts compositions.The compounding amount with (methyl) acrylate of hydroxyl is in situations more than 5 mass parts, as the adaptation of the feature of composition of the present invention, becomes better.On the other hand, compounding amount is in the situation below 50 mass parts, can suppress black compatibility and reduce.
Curing composition of the present invention is by such (A) composition and (B) combination of composition; thereby there is the excellent adaptation to plastic base and conductor circuit metal, for example, as the China ink against corrosion (anti-etching China ink, welding resistance China ink, anti-plating China ink) of use in printed circuit board, bring into play excellent substrate protective value.In addition,, even if under low exposure, also given play to excellent cured coating film characteristic.
[(C) Photoepolymerizationinitiater initiater]
As (C) Photoepolymerizationinitiater initiater, be not particularly limited, for example can use optical free radical polymerization initiator.As this optical free radical polymerization initiator, so long as utilize the generation free radicals such as light, laser, electron beam, cause the compound of Raolical polymerizable, all can use.
As optical free radical polymerization initiator, such as listing benzoin and the benzoin alkylether classes such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether; The alkyl phenyl ketone (alkyl phenone) such as 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone are, acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1, the acetophenones such as 1-dichloroacetophenone; 2-methyl isophthalic acid-[4-methyl mercapto) phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone, N, the aminoacetophenone classes such as N-dimethylamino benzoylformaldoxime; The Anthraquinones such as 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone; 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, CTX, 2, the thioxanthene ketones such as 4-diisopropyl thioxanthones; The ketal classes such as acetophenone dimethyl ketal, benzil dimethyl ketal; 2,4,5-triarylimidazoles dimer; Ribose flavine four butyric esters; The mercaptan compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; The organohalogen compounds such as 2,2,2-ethobrom, trisbromomethyl phenyl sulfone; Benzophenone, 4, benzophenone or the xanthone classes such as two (diethylamide) benzophenone of 4-; The acylphosphine oxide systems such as TMDPO, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide; Two (cyclopentadienyl group)-diphenyl titaniums, two (cyclopentadienyl group) titanium chloride, two (cyclopentadienyl groups)-bis-(2,3,4,5,6-pentafluorophenyl group) luxuriant titanium class such as titanium, two (cyclopentadienyl groups)-bis-(the fluoro-3-of 2,6-bis-(pyrroles-1-yl) phenyl) titanium etc.
These known habitual Photoepolymerizationinitiater initiaters can be used separately or use with the form of potpourri of more than two kinds, and then can add N, N-dimethylaminobenzoic acid ethyl ester, N, the light-initiated auxiliary agents such as tertiary amines such as N-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid pentyl ester, triethylamine, triethanolamine.
As commercially available Photoepolymerizationinitiater initiater, can list Irgacure261, 184, 369, 651, 500, 819, 907, 784, 2959, Darocur1116, 1173, CGI1700, CGI1750, CGI1850, CG-24-61, Lucirin TPO (more than, the trade name that BASF Japan Ltd. manufactures), DAICATII (DAICEL CHEMICAL INDUSTRIES, LTD. the trade name of manufacturing), UVAC1591 (trade name that Daicel UCP Corp. manufactures), RHODORSIL PHOTOINITIATOR2074 (trade name that Rhodia Company manufactures), EBECRY P36 (trade name that UCB Company manufactures), Esacure-KI P150, KI P65LT, KI P100F, KT37, KT55, KTO46, KI P75/B, ONE (trade name that Fratelli Lamberti Company manufactures) etc.
(C) the compounding ratio of Photoepolymerizationinitiater initiater is suitably the scope of 0.5～10 quality % of composition in its entirety.
(2 officials' energy (methyl) acrylate compounds)
Use in printed circuit board curing composition of the present invention preferably also contains except having 2 officials of hydroxyl, 2 officials' energy (methyl) acrylate compounds can (methyl) acrylate compounds.By interpolation except thering are 2 officials of hydroxyl, 2 officials' energy (methyl) acrylate compounds can (methyl) acrylate compounds, thereby can further improve the compatibility of each composition in use in printed circuit board curing composition.
Object lesson as 2 officials' energy (methyl) acrylate compounds, can list:
BDO diacrylate, 1,6-hexanediyl ester, 1,9-nonanediol diacrylate, 1, the diacrylate of the glycol such as 10-decanediol diacrylate;
Glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethyleneglycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, polypropyleneglycol diacrylate, neopentylglycol diacrylate, to at least any and the diacrylate of the glycol that obtains in neopentyl glycol addition of ethylene oxide and epoxypropane, the diacrylate of the glycol such as caprolactone modification 3-hydroxypivalic acid neopentylglycol diacrylate,
Bisphenol-A EO addition product diacrylate, bisphenol-A PO addition product diacrylate, tristane dimethanol diacrylate, hydrogenation bicyclopentadiene diacrylate, cyclohexyl diacrylate etc. have the diacrylate of ring texture etc.
As 2 commercially available officials' energy (methyl) acrylate compounds, can list Light Acrylate1, 6HX-A, 1, 9ND-A, 3EG-A, 4EG-A (trade name that common prosperity KCC manufactures), HDDA, 1, 9-NDA, DPGDA, TPGDA (DAICEL-CYTEC Company, Ltd. the trade name of manufacturing), VISCOAT#195, #230, #230D, #260, #310HP, #335HP, #700HV, #540 (trade name that OSAKA ORGANIC CHEMICAL INDUSTRY LTD. manufactures), ARONIX M-208, M-211B, M-215, M-220, M-225, M-240, M-270 (trade name that Toagosei Co., Ltd manufactures) etc.
Among them, from the viewpoint of viscosity and compatibility, preferably there is the diacrylate of glycol of the alkyl chain of carbon number 4～12, BDO diacrylate, 1 particularly preferably, 6-hexanediyl ester, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate.
As the compounding amount of these 2 functional acrylic ester compounds, in 100 mass parts compositions, be preferably 20～80 mass parts, 40～70 mass parts more preferably.The compounding amount of 2 officials' energy (methyl) acrylate is in situations more than 20 mass parts, and the compatibility of China ink becomes good.On the other hand, compounding amount is in the situation below 80 mass parts, and the adaptation of China ink becomes good.
2 officials can (methyl) acrylate compounds the viscosity at 25 ℃ be 5～50mPas, be particularly preferably 5～30mPas.In this range of viscosities, the treatability of thinning agent that can (methyl) acrylate compounds as 2 officials becomes well, can mix equably each composition.Its result, can expect to film whole in the face of substrate similarly closely sealed.
(heat curing composition)
Printing base circuit board of the present invention is with adding heat curing composition (E) in Photocurable resin composition.By adding heat curing composition (E) thus can expect that adaptation, thermotolerance improve.As the heat curing composition (E) using in the present invention, can use the known heat-curing resins such as the amino resins such as melamine resin, benzoguanamine resin, melamine derivative, benzoguanamine derivant, blocked isocyanate compounds, cyclic carbonate compound, the heat curing composition with ring-type (sulphur) ether, bismaleimides, carbodiimide resin.Viewpoint from bin stability excellence, particularly preferably is blocked isocyanate compounds.
The heat curing composition in above-mentioned molecule with a plurality of ring-types (sulphur) ether is the compound in molecule with any or 2 kinds of groups in ring-type (sulphur) ether of a plurality of 3,4 or 5 rings, for example, can list the compound in molecule with a plurality of epoxy radicals is that the compound in multi-functional epoxy compound, molecule with a plurality of oxa-cyclobutyl is that the compound in multifunctional oxetane compound, molecule with a plurality of thioether groups is episulfide resin etc.
As aforementioned multi-functional epoxy compound, can list the epoxidized vegetable oils such as Adekaiza O-130P, Adekaiza O-180A that ADEKA Co., Ltd. manufactures, Adekaiza D-32, Adekaiza D-55, the jER828 that Mitsubishi chemical Co., Ltd manufactures, jER834, jER1001, jER1004, DAICEL CHEMICAL INDUSTRIES, LTD. the EHPE3150 manufacturing, the Epiclon840 that Dainippon Ink Chemicals manufactures, Epiclon850, Epiclon1050, Epiclon2055, the EPOTOHTO YD-011 that Toto Kasei KK manufactures, YD-013, YD-127, YD-128, the D.E.R.317 that Dow Chemical Company manufactures, D.E.R.331, D.E.R.661, D.E.R.664, the Sumi-Epoxy ESA-011 that Sumitomo Chemical Company Ltd manufactures, ESA-014, ELA-115, ELA-128, the A.E.R.330 that Asahi Chemical Industry Co., Ltd manufactures, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade name) bisphenol A type epoxy resin, YDC-1312, hydroquinone type epoxy resin, YSLV-80 X Y bisphenol-type epoxy resin, YSLV-120TE thioether-type epoxy resin (being Toto Kasei KK manufactures), the jERYL903 that Mitsubishi chemical Co., Ltd manufactures, Epiclon152, Epiclon165 that Dainippon Ink Chemicals manufactures, EPOTOHTO YDB-400, YDB-500 that Toto Kasei KK manufactures, the D.E.R.542 that Dow Chemical Company manufactures, Sumi-Epoxy ESB-400, ESB-700 that Sumitomo Chemical Company Ltd manufactures, (being trade name) brominated epoxy resins such as A.E.R.711, A.E.R.714 that Asahi Chemical Industry Co., Ltd manufactures, the jER152 that Mitsubishi chemical Co., Ltd manufactures, jER154, the D.E.N.431 that Dow Chemical Company manufactures, D.E.N.438, the Epiclon N-730 that Dainippon Ink Chemicals manufactures, Epiclon N-770, Epiclon N-865, the EPOTOHTO YDCN-701 that Toto Kasei KK manufactures, YDCN-704, the EPPN-201 that Nippon Kayaku K. K manufactures, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, the Sumi-Epoxy ESCN-195X that Sumitomo Chemical Company Ltd manufactures, ESCN-220, the A.E.R.ECN-235 that Asahi Chemical Industry Co., Ltd manufactures, ECN-299 etc. (being trade name) phenolic resin varnish type epoxy resin, the xenol phenolic resin varnish type epoxy resins such as NC-3000, NC-3100 that Nippon Kayaku K. K manufactures, the Epiclon830 that Dainippon Ink Chemicals manufactures, the jER807 that Mitsubishi chemical Co., Ltd manufactures, (the being trade name) bisphenol f type epoxy resins such as EPOTOHTO YDF-170, the YDF-175 that Toto Kasei KK manufactures, YDF-2004, the bisphenol-A epoxy resins such as EPOTOHTO ST-2004, the ST-2007 that Toto Kasei KK manufactures, ST-3000 (trade name), the jER604 that Mitsubishi chemical Co., Ltd manufactures, the EPOTOHTO YH-434 that Toto Kasei KK manufactures, (being trade name) glycidyl amine type epoxy resins such as Sumi-Epoxy ELM-120 that Sumitomo Chemical Company Ltd manufactures, hydantoins type epoxy resin, DAICEL CHEMICAL INDUSTRIES, (being trade name) alicyclic epoxy resins such as CELLOXIDE2021 that LTD. manufactures, the YL-933 that Mitsubishi chemical Co., Ltd manufactures, (being trade name) trihydroxy benzene methylmethane type epoxy resin such as T.E.N., the EPPN-501 that Dow Chemical Company manufactures, EPPN-502, di-cresols or united phenol-type epoxy resin or their potpourris such as YL-6056, the YX-4000 that Mitsubishi chemical Co., Ltd manufactures, YL-6121 (being trade name), the bisphenol-s epoxy resins such as EXA-1514 (trade name) that the EPX-30 that the EBPS-200 that Nippon Kayaku K. K manufactures, ADEKA Co., Ltd. manufacture, Dainippon Ink Chemicals manufacture, the bisphenol-A phenolic varnish type epoxy resin such as jER157S (trade name) that Mitsubishi chemical Co., Ltd manufactures, four hydroxyphenyl ethane type epoxy resin such as jERYL-931 (being trade name) that Mitsubishi chemical Co., Ltd manufactures, (being trade name) hetero ring type epoxy resin such as TEPIC that Nissan Chemical Ind Ltd manufactures, the o-phthalic acid diglycidyl ester resins such as BLEMMER DGT that NOF Corp manufactures, the four glycidyl group dimethylbenzene acyl group ethane resin such as ZX-1063 (tetraglycidyl xylenoyl ethane resin) that Toto Kasei KK manufactures, ESN-190, ESN-360 that Nippon Steel Chemical Co., Ltd manufactures, HP-4032, the EXA-4750 that Dainippon Ink Chemicals manufactures, EXA-4700 etc. are containing Naphthol-based Epoxy Resin, HP-7200, the HP-7200H etc. that Dainippon Ink Chemicals manufactures have the epoxy resin of dicyclopentadiene skeleton, the glycidyl methacrylate copolymerization such as CP-50S, CP-50M that NOF Corp manufactures are epoxy resin, and then the copolymerization epoxy resin of N-cyclohexylmaleimide and glycidyl methacrylate, epoxide modified polybutadiene rubber derivant (DAICEL CHEMICAL INDUSTRIES for example, LTD. the PB-3600 manufacturing etc.), CTBN modified epoxy (YR-102, the YR-450 etc. that manufacture such as Toto Kasei KK) etc., be not limited to them.These epoxy resin can be used singly or in combination two or more.Wherein, particularly preferably phenolic resin varnish type epoxy resin, di-A type epoxy resin, united phenol-type epoxy resin, xenol phenolic resin varnish type epoxy resin, naphthalene type epoxy resin or their potpourri.
As multifunctional oxetane compound, for example, can list two [(3-methyl-3-oxa-cyclobutyl methoxy base) methyl] ether, two [(3-ethyl-3-oxa-cyclobutyl methoxy base) methyl] ether, 1, two [(3-methyl-3-oxa-cyclobutyl methoxy base) methyl] benzene of 4-, 1, two [(3-ethyl-3-oxa-cyclobutyl methoxy base) methyl] benzene of 4-, acrylic acid (3-methyl-3-oxa-cyclobutyl) methyl esters, acrylic acid (3-ethyl-3-oxa-cyclobutyl) methyl esters, methacrylic acid (3-methyl-3-oxa-cyclobutyl) methyl esters, methacrylic acid (3-ethyl-3-oxa-cyclobutyl) methyl esters, the multifunctional oxetanes classes such as their oligomer or multipolymer, and oxa-cyclobutanol and novolac resin, poly-(4-Vinyl phenol), cardo type bisphenols, calixarene kind, resorcinol calixarene kind or silsesquioxane etc. have the etherate etc. of the resin of hydroxyl.In addition, also can list and there are the unsaturated monomer of oxetanes ring and the multipolymer of (methyl) alkyl acrylate etc.
As the compound in molecule with a plurality of cyclic thioether bases, for example, can list the bisphenol A-type episulfide resin YL7000 of Mitsubishi chemical Co., Ltd's manufacture etc.In addition, also can use the episulfide resin that adopts same synthetic method the oxygen atom of the epoxy radicals of phenolic resin varnish type epoxy resin to be replaced with to sulphur atom etc.
As amino resins such as melamine derivative, benzoguanamine derivants, such as having melamine methylol compound, methylol benzoguanamine compound, methylol glycoluril compounds and hydroxymethyl urea compound etc.And then alkoxy methyl melamine compound, alkoxy methyl benzoguanamine compound, alkoxy methyl glycoluril compounds and alkoxy methyl urea compounds can obtain by the methylol of melamine methylol compound, methylol benzoguanamine compound, methylol glycoluril compounds and hydroxymethyl urea compound is separately converted to alkoxy methyl.Kind for this alkoxy methyl is not particularly limited, such as thinking methoxy, ethoxyl methyl, propoxyl group methyl, butoxymethyl etc.To human body, eco-friendly formalin concentration, be particularly preferably the melamine derivative below 0.2%.
As their commercially available product, for example can list Cymel300, Cymel301, Cymel303, Cymel370, Cymel325, Cymel327, Cymel701, Cymel266, Cymel267, Cymel238, Cymel1141, Cymel272, Cymel202, Cymel1156, Cymel1158, Cymel1123, Cymel1170, Cymel1174, Cymel UFR65, Cymel300 (is Mitsui Cyanamid Co., Ltd. manufacture), NIKALAC Mx-750, NIKALAC Mx-032, NIKALAC Mx-270, NIKALAC Mx-280, NIKALAC Mx-290, NIKALAC Mx-706, NIKALAC Mx-708, NIKALAC Mx-40, NIKALAC Mx-31, NIKALAC Ms-11, NIKALAC Mw-30, NIKALAC Mw-30HM, NIKALAC Mw-390, NIKALAC Mw-100LM, NIKALAC Mw-750LM, (be SANWA CHEMICAL CO., LTD. manufacture) etc.Such heat curing composition can be used singly or in combination of two or more.
Isocyanate compound, blocked isocyanate compounds are the compound in 1 molecule with a plurality of isocyanate group or end-blocking isocyanate group.As thering is the compound of a plurality of isocyanate group or end-blocking isocyanate group in 1 such molecule, can list polyisocyanate compound or blocked isocyanate compounds etc.It should be noted that, end-blocking isocyanate group refers to, thus isocyanate group by reacting with end-capping reagent protected temporary transient passivation group, when being heated to set point of temperature, this end-capping reagent dissociates, and generates isocyanate group.By adding above-mentioned polyisocyanate compound or blocked isocyanate compounds, confirm the raising of curability and the obdurability of the solidfied material obtaining.
As such polyisocyanate compound, for example, can use aromatic polyisocyanate, aliphatic polyisocyante or ester ring type polyisocyanates.
Object lesson as aromatic polyisocyanate, for example can list 4,4 '-methyl diphenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, phthalal diisocyanate, m-phenylenedimethylim-diisocyanate and 2,4-toluene diisocyanate dimer etc.
Object lesson as aliphatic polyisocyante, can list tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethyl hexamethylene diisocyanate, 4,4-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) and isophorone diisocyanate etc.
As the object lesson of ester ring type polyisocyanates, can list bicycloheptane triisocyanate.And the adduct of the isocyanate compound listing above, biuret body and isocyanuric acid ester body etc.
As blocked isocyanate compounds, can use the addition reaction product of isocyanate compound and isocyanate-terminated dose.As the isocyanate compound that can react with end-capping reagent, for example, can list above-mentioned polyisocyanate compound etc.
As isocyanate-terminated dose, such as listing the phenol such as phenol, cresols, xylenols, chlorophenol and ethyl-phenol, be end-capping reagent; The lactams such as epsilon-caprolactams, δ-valerolactam, butyrolactam and azetidinone are end-capping reagent; Ethyl acetoacetate and diacetone isoreactivity methylene base system end-capping reagent; The alcohol such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzylic ether, methyl glycollate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate are end-capping reagent; The oximes such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monoxime, hexamethylene oxime are end-capping reagent; The mercaptan such as butyl mercaptan, hexyl mercaptan, tert-butyl mercaptan, benzenethiol, methylbenzene phenyl-sulfhydrate, ethyl thiophenol are end-capping reagent; The acid amides such as acetamide, benzamide is end-capping reagent; The imide series such as succinimide and maleimide end-capping reagent; The amine such as xylidin, aniline, butylamine, dibutylamine are end-capping reagent; The imidazoles such as imidazoles, 2-ethyl imidazol(e) are end-capping reagent; The imines such as methylene imine and propylidene imines are end-capping reagent etc.
Blocked isocyanate compounds can be also commercially available material, for example, can list Sumidule BL-3175, BL-4165, BL-1100, BL-1265, Desmodule TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotherm2170, Desmotherm2265 (is Sumika Bayer Urethane Co., Ltd. manufacture), Coronate2512, Coronate2513, Coronate2520 (being Nippon Polyurethane Industry Co., Ltd. manufactures), B-830, B-815, B-846, B-870, B-874, B-882 (is Mitsui Takeda Chemical Co., Ltd. manufacture), TPA-B80E, 17B-60PX, E402-B80T (being Asahi Kasei Chemicals Corporation manufactures) etc.It should be noted that, Sumidule BL-3175, BL-4265 are used the first and second oximes to obtain as end-capping reagent.The compound in 1 molecule like this with a plurality of isocyanate group or end-blocking isocyanate group can be used singly or in combination of two or more.
The compounding amount of such Thermocurable composition is preferably 1～30 mass parts with respect to the aforementioned whole compositions of 100 mass parts.If more than compounding amount 1 mass parts, can access the enough obdurability of filming, thermotolerance.On the other hand, if below 30 mass parts, can suppress bin stability and reduce.
In use in printed circuit board curing composition of the present invention, except mentioned component, compounding surface tension modifier as required, surfactant, matting agent, for adjusting the polyester based resin of film physical property, polyurethane series resin, vinyl resin, acrylic resin, rubber series resin, wax class, phthalocyanine blue, phthalocyanine green, iodine is green, dual-azo yellow, crystal violet, titanium dioxide, carbon black, the known habitual colorants such as naphthalene black (naphthalene black), silicon-type, fluorine system, in the defoamer of macromolecular etc. and levelling agent at least a kind, imidazoles system, thiazole system, triazole system, the known habitual additive kind that the adaptation imparting agents such as silane coupling agent are such.
The use in printed circuit board curing composition of the present invention with above-mentioned each composition can be applied to the printing processes such as silk screen print method, ink-jet method, dip coating, flow coat method, rolling method, excellent painting method, curtain Tu Fa.Particularly in the situation that being applied to ink-jet method, the viscosity at 50 ℃ is preferably 5～50mPas, is particularly preferably 5～15mPas.The printing that can be well on thus, and can not apply unnecessary load to ink-jet printer.
In the present invention, viscosity refers to the viscosity of measuring at normal temperature (25 ℃) or 50 ℃ according to JIS K2283.If for the viscosity below 150mPas or at 50 ℃ is 5～50mPas, can utilize ink jet printing method printing under normal temperature.
And then, the China ink that use in printed circuit board curing composition of the present invention is used as ink-jetting style based on above-mentioned composition and in situation about applying, can carry out to flexible PCB the printing of roll-to-roll formula.Now, by after by ink-jet printer, aftermentioned irradiation light source being installed, thereby can form at high speed corrosion-resisting pattern.
The irradiation of irradiation utilization ultraviolet ray or active-energy is carried out, preferably ultraviolet ray.As light-struck light source, be suitably low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp, metal halide lamp etc.In addition, also can utilize electron beam, alpha ray, β ray, gamma-rays, X ray, neutron beam etc.And then after irradiation, utilize as required heating to be cured.At this, heating-up temperature is for example 80～200 ℃.By being made as described heating-up temperature scope, thereby can solidify fully.Heat time is for example 10～100 minutes.
And then, use in printed circuit board curing composition of the present invention can form for comprise polyimide etc. as the plastic base of principal ingredient and the adaptation of the printed circuit board (PCB) of the conductor circuit arranging thereon excellent, and the pattern cured of each excellent such as resistance to sweating heat performance, chemical proofing, pencil hardness, the gold-plated property of chemically-resistant, bending property is filmed.
embodiment
Embodiment is below shown the present invention is specifically described, but the present invention is not only defined in these embodiment.It should be noted that, if do not have below specified otherwise " part " mean mass parts.
embodiment 1～11 and comparative example 1～3
Composition with shown in the ratio shown in table 1 (unit: part) compounding table 1, carries out premixed, prepares curing composition with stirring machine.
The curing composition of making for above-mentioned such operation with and character below cured coating film evaluation.
1. the compatibility of curing composition
The anti-corrosion agent composition being obtained by embodiment 1～11 and comparative example 1～3 is sealing in transparent vial, then standing 1 week, by Visual Confirmation, has or not separation.The benchmark of evaluating is as described below.
Zero: do not have separated and transparent
△: there is no separation but muddiness
*: produce separated
In measurement result shown in table 2.
dry to touch after 2.UV solidifies
Use the coating device (manufacture of ERICHSEN company) of 30 μ m that the use in printed circuit board curing composition being obtained by embodiment 1～11 and comparative example 1～3 is applied to polyimide base material (UPILEX25S) above, utilize high-pressure sodium lamp (ORC Co., Ltd. manufactures HMW-713) with 150mJ/cm
2be cured.
Zero: inviscid
*: exist glutinous greasy
In measurement result shown in table 2.
3. with the adaptation of polyimide
Use the coating device (manufacture of ERICHSEN company) of 30 μ m that the curing composition being obtained by embodiment 1～11 and comparative example 1～3 is applied to polyimide base material (UPILEX25S) above, utilize high-pressure sodium lamp (ORC Co., Ltd. manufactures HMW-713) with 150mJ/cm
2be cured.Then, with the heated air circulation type drying oven of 150 ℃, carry out 60 minutes heat treated.The sample of making is implemented to cross-hatching belt stripping test (cross-cut tape peel test) (JIS K5600).
Zero: do not peel off
*: exist and peel off
In measurement result shown in table 2.
4. with the adaptation of copper
Use the coating device (manufacture of ERICHSEN company) of 30 μ m that the curing composition being obtained by embodiment 1～11 and comparative example 1～3 is applied on Copper Foil, utilize high-pressure sodium lamp (ORC Co., Ltd. manufactures HMW-713) with 150mJ/cm
2be cured.Then, with the heated air circulation type drying oven of 150 ℃, carry out 60 minutes heat treated.The sample of making is implemented to cross-hatching belt stripping test (cross-cut tape peel test).
Zero: do not peel off
*: exist and peel off
In measurement result shown in table 2.
viscosity at 5.50 ℃
With cone-plate type viscosity meter (Toki Sangyo Co., Ltd. manufacture TVH-33H), measure the curing composition that obtained by embodiment 1～11 and comparative example 1～3 viscosity under 50 ℃, 100rpm.
Viscometric result is, in the scope in 5～50mPas, has embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6, embodiment 7, embodiment 8, embodiment 11, comparative example 1, comparative example 2, a comparative example 3.
6. resistance to bending
Preparation utilizes the copper wiring (Wiring pattern) of the Kapton of thickness 25 μ m and the comb shape being formed by Copper Foil of thickness 12 μ m and the flexible copper-clad laminated plate (width=200 μ m/200 μ m between length 110mm, width 60mm, copper wiring width/copper wiring) that forms.Using piezo-electric type ink-jet printer by ink jet printing, on the substrate of this flexible copper-clad laminated plate, to take the mode that thickness is 15 μ m is coated with.Now, after printing, utilizing immediately the incidental high-pressure sodium lamp of ink gun to carry out UV temporarily solidifies.Then, thereby heat at 150 ℃, within 1 hour, make it solidify, obtain test film.For the test film after solidifying; use MIT (Massachusetts Institute of Technology (MIT); Massachusetts Institute of Technology) testing machine (peace field essence mechanism make manufacturing No.307) repeats to implement bending diaphragm is become to the mode of inner side under the following conditions, obtain no longer can conducting period.Every evaluation for 1 time implemented test to 3 test films, calculate no longer can conducting mean value.Test condition and metewand are as described below.
The test condition of resistance to MIT
Load: 500gf
Angle: 135 ° of bending angles
Speed: 175 beats/min
Front end: R0.38mm cylinder
Metewand
More than zero: 100 time
△: 50 above and less thaies 100 times
*: less than 50 times
7. solvent resistance
Cured coating film substrate manufacture condition by 4. being obtained by visualization floods the painting membrane stage after 30 minutes in acetone, with following benchmark, evaluates.
Metewand
Zero: do not observe any variation.
△: only slightly change (albefaction).
*: observe the swelling of filming or peel off.
8. chemical proofing
Cured coating film substrate manufacture condition by 4. being obtained by visualization floods the painting membrane stage after 10 minutes in the aqueous sulfuric acid of 5wt%, with following benchmark, observes.
Metewand
Zero: do not observe any variation.
△: only slightly change (albefaction).
*: observe the swelling of filming or peel off.
9. resistance to sweating heat performance
The cured coating film that substrate manufacture condition by 4. is obtained floods after 10 seconds according to the method for JISC-5012 in the solder bath of 260 ℃, utilize viscose paper adhesive strip to carry out disbonded test, then by visualization, it is coated with membrane stage, with following benchmark, evaluates.
Metewand
Zero: film and do not change.
△: film and change.
*: film and peel off.
10. chemically-resistant plates property
Use commercially available electroless nickel bath and chemical gilding to bathe, under the condition of nickel 0.5 μ m, golden 0.03 μ m, carry out plating, the cured coating film that the substrate manufacture condition by 4. is obtained carries out gold-plated, is cured the observation of film coated surface state.Determinating reference as described below.
Metewand
Zero: do not observe any variation.
△: only slightly change.
*: produce significantly albefaction or send out mist.
table 1
ProductName in table 1 and abridge as described below.
EY RESIN BR-45UAS: the IPDI of polybutadiene diol (isophorone diisocyanate) modified amido formic ether acrylate (Light Chemical Industries Co., Ltd. manufactures)
BAC-45: propylene acidylate butadiene (molecular weight approximately 10000) (OSAKA ORGANIC CHEMICAL INDUSTRY LTD. manufacture)
Light Acrylate1,9-NDA:1,9-nonanediol diacrylate (Kyoeisha Chemical Co., Ltd.'s manufacture)
Light Ester HO-250: HEMA (Kyoeisha Chemical Co., Ltd.'s manufacture)
4HBA: acrylic acid 4-hydroxy butyl ester (Nippon Kasei Chemical Co., Ltd manufactures)
Darocur1173:2-hydroxy-2-methyl-1-phenyl-propane-1-ketone (BASF Japan Ltd. manufacture)
2-ethyl AQ:2-EAQ (BASF Japan Ltd. manufacture)
Irgacure819: two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide (BASF Japan Ltd. manufacture)
Lucirin TPO:2,4,6-trimethylbenzoyl diphenyl phosphine oxide (BASF Japan Ltd. manufacture)
BI7982: blocked isocyanate (manufacture of Baxenden company)
BYK-307: silicon-type adjuvant (BYK Japan Co., Ltd. manufactures, surface tension modifier)
table 2
As shown in table 2, the dry to touch of the use in printed circuit board curing composition of embodiments of the invention 1～11 after the compatibility of curing composition, UV solidify, and the adaptation of polyimide, and the adaptation of copper, pencil hardness, bending, solvent resistance, chemical proofing, resistance to sweating heat performance, the gold-plated property of chemically-resistant aspect all show good result.
Particularly, in also used embodiment 1～8, the embodiment 11 of 2 officials' energy (methyl) acrylate compounds (D composition) except composition A～C, the compatibility of each composition in use in printed circuit board curing composition is extremely excellent, can access stable film performance.
On the other hand, lack in any one the comparative example 1～3 in composition A of the present invention, B, can not get enough film performances aspect the adaptation after the adaptation of polyimide substrate or UV are solidified.
The present invention is not limited to formation and the embodiment of above-mentioned embodiment, in the scope of the purport of inventing, can carry out various distortion.
utilizability in industry
As described above, use in printed circuit board curing composition of the present invention can form the adaptation of plastic base and conductor circuit metal excellent, and the fine pattern of each excellent such as resistance to sweating heat performance, solvent resistance, chemical proofing, pencil hardness, the gold-plated property of chemically-resistant.
In addition,, while spraying with ink-jetting style, in order to spray, must be made as low viscosity.It is low that common low viscous curing composition is regarded as the characteristics such as adaptation/thermotolerance, even if but this composition is low viscosity, also can be aptly for the soldering-resistant pattern that utilizes ink-jetting style of printed circuit board (PCB), forms.Therefore, except the printed wiring materials such as China ink against corrosion, mark China ink, can also be for such as UV products formed material, material, 3D purposes such as material for ink-jet for light chisel.
Claims (11)
1. a use in printed circuit board curing composition, is characterized in that, comprises:
(A) have polyenoid skeleton (methyl) acrylate compounds,
(B) have hydroxyl (methyl) acrylate compounds and
(C) Photoepolymerizationinitiater initiater.
2. use in printed circuit board curing composition according to claim 1, wherein, the polyenoid skeleton that described (A) has in (methyl) acrylate compounds of polyenoid skeleton is formed by the polymerization of butadiene and/or isoprene.
3. use in printed circuit board curing composition according to claim 2, wherein, the repetitive of polyenoid skeleton that described (A) has (methyl) acrylate compounds of polyenoid skeleton represents by general formula (I),
In formula, n represents 10～300.
4. according to the use in printed circuit board curing composition described in any one in claim 1～3, wherein, also contain except thering are 2 officials of hydroxyl, 2 officials' energy (methyl) acrylate compounds can (methyl) acrylate compounds.
5. use in printed circuit board curing composition according to claim 4, wherein, described be 5～50mPas except having the viscosity of 2 officials' energy (methyl) acrylate compounds at 25 ℃ of 2 officials of hydroxyl can (methyl) acrylate compounds.
6. according to the use in printed circuit board curing composition described in any one in claim 1～5, wherein, also comprise heat curing composition.
7. according to the use in printed circuit board curing composition described in any one in claim 1～6, wherein, the viscosity at 50 ℃ is 5～50mPas.
8. a cured coating film, is characterized in that, carries out irradiation obtain by the use in printed circuit board curing composition to described in any one in claim 1～7.
9. a printed circuit board (PCB), is characterized in that, has pattern cured and films, and described pattern cured is filmed and obtained by the use in printed circuit board curing composition described in any one in claim 1～7 is printed onto on substrate and it is carried out to irradiation.
10. a printed circuit board (PCB), it has pattern cured films, and described pattern cured is filmed and is obtained by utilizing ink jet printing method that the use in printed circuit board curing composition described in any one in claim 1～7 is printed onto on substrate and it is carried out to irradiation.
11. according to the printed circuit board (PCB) described in claim 9 or 10, and wherein, described substrate is plastic base.
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| JP2013-074507 | 2013-03-29 | ||
| JP2013-243864 | 2013-11-26 | ||
| JP2013243864A JP5653508B2 (en) | 2013-03-29 | 2013-11-26 | Curable composition for printed wiring board, cured coating film using the same, and printed wiring board |
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| CN104076605B CN104076605B (en) | 2016-10-12 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106795397A (en) * | 2014-09-16 | 2017-05-31 | 株式会社Lg化学 | Adhesive composition, optical bonding film and touch panel for touch panel |
| CN109154773A (en) * | 2016-05-31 | 2019-01-04 | 富士胶片株式会社 | Photosensitive polymer combination, transfer film, decorative pattern and touch panel |
| CN112739048A (en) * | 2020-12-10 | 2021-04-30 | 厦门柔性电子研究院有限公司 | Roll type manufacturing method of double-sided flexible circuit board and flexible circuit board manufactured by same |
| CN116323204A (en) * | 2020-10-07 | 2023-06-23 | 株式会社大赛璐 | Curable composition and cured product thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5968291B2 (en) | 2013-09-30 | 2016-08-10 | 太陽インキ製造株式会社 | White curable composition for printed wiring board, cured coating film using the same, and printed wiring board |
| FR3111637B1 (en) * | 2020-06-18 | 2022-09-02 | Arkema France | COMPOSITIONS AND METHODS FOR FORMING 3D PRINTABLE MATERIALS CAPABLE OF LOW DIELECTRIC LOSS |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10224018A (en) * | 1997-01-31 | 1998-08-21 | Shikoku Chem Corp | Resist ink for flexible printed wiring board |
| JP2011057751A (en) * | 2009-09-07 | 2011-03-24 | Chisso Corp | Polymerizable composition |
| JP2011088975A (en) * | 2009-10-21 | 2011-05-06 | Hitachi Chem Co Ltd | Photocurable moisture-proof insulating coating material and method for manufacturing moisture-proof insulated electronic part using the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2624723B2 (en) | 1987-11-04 | 1997-06-25 | 宇部興産株式会社 | Polyimide composition for printing |
| JP2982420B2 (en) | 1991-09-13 | 1999-11-22 | 日本電気株式会社 | Semiconductor integrated circuit device |
| JP3190251B2 (en) | 1995-06-06 | 2001-07-23 | 太陽インキ製造株式会社 | Photocurable and thermosetting resin composition for alkali-developed flexible printed wiring boards |
| TWI464210B (en) * | 2005-07-08 | 2014-12-11 | Toray Industries | Resin composition and molded article composed of the same |
-
2013
- 2013-11-26 JP JP2013243864A patent/JP5653508B2/en active Active
-
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- 2014-03-20 KR KR1020140032729A patent/KR20140118794A/en active Application Filing
- 2014-03-27 US US14/227,249 patent/US9265156B2/en active Active
- 2014-03-27 TW TW103111495A patent/TWI498397B/en active
- 2014-03-28 CN CN201410124536.4A patent/CN104076605B/en active Active
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10224018A (en) * | 1997-01-31 | 1998-08-21 | Shikoku Chem Corp | Resist ink for flexible printed wiring board |
| JP2011057751A (en) * | 2009-09-07 | 2011-03-24 | Chisso Corp | Polymerizable composition |
| JP2011088975A (en) * | 2009-10-21 | 2011-05-06 | Hitachi Chem Co Ltd | Photocurable moisture-proof insulating coating material and method for manufacturing moisture-proof insulated electronic part using the same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106795397A (en) * | 2014-09-16 | 2017-05-31 | 株式会社Lg化学 | Adhesive composition, optical bonding film and touch panel for touch panel |
| CN106795397B (en) * | 2014-09-16 | 2021-02-23 | 株式会社Lg化学 | Adhesive composition for touch screen panel, optical adhesive film, and touch screen panel |
| CN109154773A (en) * | 2016-05-31 | 2019-01-04 | 富士胶片株式会社 | Photosensitive polymer combination, transfer film, decorative pattern and touch panel |
| CN109154773B (en) * | 2016-05-31 | 2022-04-12 | 富士胶片株式会社 | Photosensitive resin composition, transfer film, decorative pattern, and touch panel |
| US11500286B2 (en) | 2016-05-31 | 2022-11-15 | Fujifilm Corporation | Photosensitive resin composition, transfer film, decorative pattern, and touch panel |
| CN116323204A (en) * | 2020-10-07 | 2023-06-23 | 株式会社大赛璐 | Curable composition and cured product thereof |
| CN112739048A (en) * | 2020-12-10 | 2021-04-30 | 厦门柔性电子研究院有限公司 | Roll type manufacturing method of double-sided flexible circuit board and flexible circuit board manufactured by same |
Also Published As
| Publication number | Publication date |
|---|---|
| US9265156B2 (en) | 2016-02-16 |
| JP5653508B2 (en) | 2015-01-14 |
| KR20140118794A (en) | 2014-10-08 |
| US20140290990A1 (en) | 2014-10-02 |
| JP2014209542A (en) | 2014-11-06 |
| TW201446898A (en) | 2014-12-16 |
| TWI498397B (en) | 2015-09-01 |
| CN104076605B (en) | 2016-10-12 |
| KR101684212B1 (en) | 2016-12-07 |
| KR20160023738A (en) | 2016-03-03 |
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